How Ions Break Local Symmetry: Simulations of Polarized Transient Hole Burning for Different Models of the Hydrated Electron in Contact Pairs with Na +
How Ions Break Local Symmetry: Simulations of Polarized Transient Hole Burning for Different Models of the Hydrated Electron in Contact Pairs with Na +
复制标题
离子如何打破局部对称性：模拟与 Na 接触对的水合电子的不同模型的极化瞬态烧孔
DOI：
10.1021/acs.jpclett.3c00220
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Schwartz, Benjamin J.
中科院分区：
文献类型：
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作者：
Park, Sanghyun J.;Schwartz, Benjamin J.
通过极化瞬态烧孔（pTHB）实验可知水合电子（eaq–）具有均匀展宽的吸收光谱。在这里，我们通过量子模拟探索不同 eaq 模型的 pTHB 光谱在电解质存在下如何变化。这个想法是，阳离子-eaq-配对可以打破局部对称性，从而导致持续的不均匀性。我们发现，“硬”腔模型显示，在盐存在的情况下，pTHB 恢复时间略有增加，而“软”腔模型则保持均匀加宽，与盐浓度无关。我们还探索了基于完全ab初始密度泛函理论的eaq模型的取向各向异性，该模型在没有盐的情况下会强烈不均匀地展宽，并且在存在盐的情况下会变得更加不均匀地展宽。这些结果为可以区分不同模型的实验提供了直接预测，从而有助于确定 eaq- 的水合结构和动力学。
The hydrated electron (eaq–) is known via polarized transient hole-burning (pTHB) experiments to have a homogeneously broadened absorption spectrum. Here, we explore via quantum simulation how the pTHB spectroscopy of different eaq–models changes in the presence of electrolytes. The idea is that cation–eaq–pairing can break the local symmetry and, thus, induce persistent inhomogeneity. We find that a “hard” cavity model shows a modest increase in the pTHB recovery time in the presence of salt, while a “soft” cavity model remains homogeneously broadened independent of the salt concentration. We also explore the orientational anisotropy of a fullyab initiodensity functional theory-based model of the eaq–, which is strongly inhomogeneously broadened without salt and which becomes significantly more inhomogeneously broadened in the presence of salt. The results provide a direct prediction for experiments that can distinguish between different models and, thus, help pin down the hydration structure and dynamics of the eaq–.